Ultraviolet sensitive print-out compositions and process for image-wise exposure and fixing of same



United State P t o,,

ULTRAVIOLET snNsrrrvii PRINT-OUT COMPOSI- rrous AND rnocass FOR IMAGE-WISE EX- POSURE AND FIXING'OF SAME' 3,164,467 Patented Jan. 5, 1965 2 possess sufiicierit blue-absorption or for other reasons, notedbelow. v r 7 In obtaining the..resuits ,tabulated in. Table I carbon tetrabromide and either indole or substituted indole or RobertH spmgue, Chagrin Falls, and Morris C. Roscow, 5 substituted pyrrole were dissolved in a mixture of aee Cleveland, (lhio, assignors to Horizons Incorporated, ton? and ethyl acetate 9 9 solutlon a corporation of New Jersey e was coated on Myla-r 303-D w1th a Bird applicator and No Drawing Filed 14, 1963, s 2 5,079 dried at room temperature as described in the article 11 Cl ims, (Cl, 96-48) noted above and then-through a silver step wedge exa posed to 1,2 or 5 General Electric Sunlamps at 12 inches This invention relates to, a new ultraviolet sensitive for between .8 and '12 minutes. After exposure the films print-out film. More particularly it relates to improvewere fixed in a forced draft oven at 100? C. for three ments over the ultraviolet sensitive print-out film deminutes. Then the 'optical density'was read through the scribed in United States Patent 3,042,515 and in the filter indicated withadensitometer. i

TABLE I Coating Conditions and Maximum Densities Obtained Coating Components 1 Exposure, G.E. Sun- Density at 21st Steplamps 3 (12 in. distance) Coating I I No. 7 Color of Image Amt, CBri, Under Under Under Dye Former gm. gm No, Lamps Minutes Blue Green Red Filter Filter Filter Diphenylamine 0.6 0. 7 8 0. 53 1. 67 2. 60 Blue. Indole 0. 5 0. 7 s 2. 10 1. 0. Yellow. 0.5 0.7 a 2.40 1.40 0.30 D0. 0.5 1.4 s 2.27 1.28 a 0.26 Do. 0. 5 2.1 s 1 Did not dry. Do.

. Density not read. 0.75 1.4 s 2.70 1.45 0.28 Do. 0. 5 0. 7 1o 2. 20 Do. 0.7 0.7 10 2.45 Do. 0.9 0.7 10 2.55 Do. 1.1 0.7 10 2.70 Do. 0. 0. 7 10 1. 55 1. 0. 22 Orange 0.61 0.7 8% 1.10 2.00 Pink. 0.80 0.7 8% 0.75 1.15 0.95 Blue. 0.60 0.7 I 8% 1.11 0.76 0.14 Yellow. 0. 55 0. 7 s 0. 55 0.70 0. 55 Black. Skatole 0.7 1.4 s 0.85 0. 93 0.52. Do. I 2,5-dimethyl-l-phenylpyrrole 0. 5 1. 0 12 1. 30 0. 46 0. 21 Yellow. 2,4dimethyl-3-ethylpyrrole 0. 09 0. 7 12 3+ 2. 66 1. 27 Brown-black.

1 For each coating the 013m and Dye Former were dissolved in a mixture consisting of 5.0 cc. of acetone and 3.0 cc. of ethyl acetate. 2 All coatings were 0.0015 wet thickness except Nos. 1, 3, 17 and 18 which were 0.0030 inch wet thiclmess.

For output of these lamps see U.S. Patent 3,046,209. I r Photographic Science and Engineering, volume 5, pages 98-103 (1961). i

Although the diphenylamine/ carbon tetrabromide material described in theabove references yields satisfactory prints in many applications, the bule color has been found to be unsuitable for subsequent printing on color blind film, its low blue absorption resulting in very low contrast prints.

Specifically the present invention is directedparticularly to ultraviolet sensitive print-out film in which blue absorbing images e.g. yellow or black images ,are readily produced.

Photosensitive compositions containing carbon tetra.- bromide and indoles or pyrroles as the organic amineare disclosed in the United States Patent 3,056,673, is sued October 2, 1962, to Eugene Wainer. The ultraviolet sensitive print-out films constituting the present invention are based on specific indoles with or without specific accelerators, possessing improved properties over those disclosed in said patent. 1

Not all indoles are suitable for the present intended purpose, either because the image obtained does not Results shown in Table I are illustrative of the effects of varyingexposure, concentration or the relative proportions of CBr, to various dye formers including indole, substituted indoles or pyrroles. Although 3-methylin-dole (Skatole) .has a very objectionable, extremely rank odor, it gives by far the highest quality black images of any of the indoles. In practice any unreacted skatole would be removed from the film by a solvent rinse or by other suitable treatment. The 2,4-dimethyl-3- ethylpyrrole also gave a black image, although the fog level was very'high, due to the oxidation by air during the heat-fixing step, characteristic of certain classes of pyrroles.

Substitution of indole-3-carboxaldehyde for indole in the above indole/carbon tetrabromide formula gave a composition with practically no photographic response V 7 creases the speed of the indole-carbon tetr abromide compositions. I

Substitution of 2-methyl-3-indolealdehyde for indole in the formula gave greatly reduced density on exposure and the addition of 2-methyl-3-indolealdehyde to the indole mixture did notinorease the density obtained upon exposure. Image color and background color were similar to the color formed in exposed film without the addition of this compound.

Replacement of indole by 3-acetylindole resulted in considerable loss of speed in the composition although coatings prepared from compositions with both indole and B-acetylindole were.very similar to those of the indole color in imagecolor and background. having approximately the samespeed and density.

These resultsvmay' be summarized as follows.

over indole.

The efiectiveness of other indole compounds and combinations of indoles were investigated, using a mixture of cc. of methylisobutyl ketonev and3 cc. of isopropyl acetate as the solvent for the carbon tetrabrornide, the dye former (diphenylamine or indole compound) and the accelerator when one was used. I

The solution so formed was coated with a Bird water using a wet film thickness of 0.0015 inch on Mylar 3'02-T. After being dried at room temperature films were exposed to the light of two G.E. Sunla' riips at a distance of twelve inches for ten minutes through a Kodak #2 silver step wedge. After exposure the optical density of the area In the tabulated results reported in Table III, numbers 1-17 represent the results obtained when compositions consisting of the indicated weights of CBr and the dye former were exposed; numbers 18-34 represent similar compositions except that indole has been added thereto in the amounts indicated; and compositions35-38 illustrate compositions wherein the constituents are CBr a substituted indole and indole-3-carboxaldehyde as the accelerator.

In Table III the specific compounds used were as follows: 7 r

No. Dye Former Indole.

lndole 3-carboxylic acid.

' Indole-3-butyric acid.

5-cyan0'in'dole.

4-chloroindole.

fi-chloroindole.

fi-bror'noindole. 5-bromoindole-3carboxaldehyde. 5-chloro-3-methyl indole. 3-phenylind0le.

V Indo1e-3-carbino1.

5-phenyl-3-methylindole. Ethyl-3-indole acetate. 3-dimethylaminomethylindole. 1-methyl-2-phenylindole.

N-plienylpyrrole.

- N-methylpyrrole-2-aldehyde.

Accelerator Indole-3-carboxaldehyde. IindoleB-carboxylic acid. Indole-3acetic acid. Indole-3-pr0pionic acid. Indole'3-butyrio acid. fi-cyanoindo. 5-eyauoindo1 and Indole-E-carboxaldehyde. 4-chloroindole. 5-chloroindo1e. 5-bromoiudole 3-carboxaldehyde. Indole-B-carbinol. Indole-3-carboxaldehyde and 1- ethyloxindole.

Ethyl-3-indole acetate. 3-dimethylarninomethylindole. l-methyl-Z-phenylindole. N-phenylpyrrole. I N-methylpyrrole-Z-aldehyde. Indo1e-3-carboxaldehyde.

v I 5-broinoindole Do. printed at the twenty first or most transparent step of 37 5-p g f' y the wedge and optical density of the background were 38 5 Do measured with a photo volt densrtometer. Results are methy shown in Table III.

TABLE III Weight in Grams. Color Blue Filter Number No. of Steps Dye Visible Density Density of 013m Former Image Background ot21st Base+Fog 0. 9 0. 5 Oran e Clear 13 2. 0'5 0. 03 0.9 0.5 Magenta; Magenta 13 1. 57 0.37 0.9 0. 5 81 8 0.21 0.03 0.9 0.6 7 0. 51 0.03 0.9 0. 64 Red-Orange 7 0. 42 0.03 0. 9 0. 64 Orantie 12 I. 58 O. 03 0.9 0.85 do d0 13 1.82 0.03 0.9 .05 No image f l 0.9 v 0.62 Fades to pale tan on .do 4 0.18 0.03 heating. v I O. 9 0. 8 8 0. 27 0. 03 0. 7 0; 1 7 0. 52 0. 24 0. 9 0. 88 13 0. 0. 03 0. 9 0.5 Print, Blue, 0 pale 4 0. 16 0.03

Green-Yellow on heate. 0.9 0.25 Very faint tan 4 0. 11 0. 03 0. 9 0. 5 B1ue r 13 0. 52 0. 03 l 0. 9 0. 62 Blue to Olive d.o 13 0.29 0. 03 4 0.9 0. 46 No Color TABLE In -Continued Accel- CBn Indole erator Background Blue-Blaek Very faint pink.

Blue Filter Number of Steps Visible Density Density of of 21st Base+ Step Fog j 1 Dye former not indole, see list.

From the foregoing it will be seen that in order to obtain an image with good blue absorption characteristics, in a film having no objectionable background color and possessing good speed and density, the following are required in the composition:

Activat0r.-Carbon tetrabromide or other compound represented by the general formula RCBr wherein R represents a member selected from the group consisting of Br, alkyl, bromoalkyl, aroyl, aryl and aralkyl and R is selected so that the compound is normally solid at room temperature. Suitable compounds include carbon tetrabnomide, pentabromoethane, hexabromoethane, (1,11,11- benzotribromide, p-nitrobenzotribromide and tribromoacetophenone. Mixtures of such compounds may be used in the same manner as the individual compounds.

Dye f0rmer.-3-methylindole, 5-phenyl-3-methylindole or indole plus one of the following:

Indole-3-carboxaldehyde 5 -bromoindole-3-carboxaldehyde 1-methyl-2-phenylindole N-phenyl pyrrole Carrier.-ethyl acetate, isopropyl acetate, or any film forming plastic compatible with the other constituents may be used when the constituents are to be used in the form of a thin dry self supporting film in which they are dispersed uniformly. Otherwise, the mixture may be applied as a solution to any suitable substrate such as paper or any other inert base and the solvent evaporated therefrom. In the examples above the numbers 303D and 302T refer to a subbed Mylar polyester found to be particularly well suited for the present invention.

Pr0p0rti0ns.For each part by weight of indole, 3- methylindole, or 5-phenyl-3-methylindole, between 0.5 and 10.0 parts of CBr or other polybromine organic free radical source and from about 0.001 to 0.5 part by weight of activator when used per part by weight of dye former, about 0.05 to 0.2 part by weight of activator per part of dye former being preferred when the dye former is indole.

Having now described this invention in accordance with the patent statutes it is not intended that it be limited except as required by the appended claims.

1. A composition printing out an image directly when exposed to a suitable dosage of ultraviolet, said image exhibiting relatively good blue absorption, said composition being physically supported in an inert carrier and said composition consisting essentially of (1) at least one organic bromine compound selected from the group consisting of compounds represented by the general formula wherein R is selected from the group consisting of Br, alkyl, aryl, aralkyl, and aroyl such that the compound is normally a solid at room temperature and (2) an indole compound selected from the group consisting of 3-methylindole, 3-methyl-5-phenylindole and mixtures of indole with at least one substituted indole selected from the group consisting of indole-3-carboxaldehyde, S-bromoindole-S- car-boxaldehyde, 1-methyl-2-phenylindole and N-phenyl pyrrole; there being between 0.5 and 10 parts by weight of said organic bromine compound for each part by weight of said indole compound and indole in said composition.

2. The composition of claim 1 uniformly dispersed in a film forming plastic.

3. The composition of claim 1 coated onto a synthetic polymer sheet.

4. A composition printing out an image directly when exposed to a suitable dosage of ultraviolet, said image exhibiting relatively good blue absorption, said com-position being physically supported in an inert carrier and said composition consisting essentially of (l) at least one organic bromine compound selected from the group consisting of compounds represented by the general formula wherein R is selected from the group consisting of B1, alkyl, aryl, aralkyl, and aroyl such that the compound is normally a solid at room temperature and (2) 3-methyl- S-phenylindole; there being between 0:5 and 10 parts by weight of said organic bromine compound for each part by weight of 3-methyl-5-phenyl indole in said composition.

5. The composition of claim 4 wherein the bromine compound is a brominated lower alkane selected from the group consisting of methane and ethane.

6. The composition of claim 5 :wherein the bromine compound is CBr 7. A composition printing out an image directly when exposed to a suitable dosage of ultraviolet, said images exhibiting relatively good blue absorption, said composition being physically supported in an inert carrier and said composition consisting essentially of ('1) at least one organic bromine compound selected from the group consisting of compounds represented by the general formula wherein R is selected from the group consisting of Br, alkyl, aryl, aralkyl, and aroyl such that the compound is normally a solid at room temperature and (2) 3-methylindole; there being between 0.5 and 10 parts by weight of said organic bromine compound for each part by weight of 3-methyl indole in said composition.

8. The composition of claim 7 wherein the bromine being physically supported in an inert carrier and said composition'consisting essentially of (l) at least one organic bromine compound selected trom the group consisting of compounds represented by the general formula wherein R is selected from the group consisting of Br, alkyl, aryl, aralkyl, and aroyl such that the compound is normally a solid at room temperature and (2) a mixture of indole and indole-S-carboxaldehyde, there being about 10 parts of indole by weight for each part of indole-3- carboxaldehyde in said mixture and between about 0.5 and 10 parts 'by weight of said organic'bromine compound for each part by weight of indole in said composition.

11. The process which comprises preparing the composition of claim 1 in a thin dry layer, photographically exposing said composition to a dosage of ultraviolet radiation and fixing the resultant image by heat,

References Cited by the Examiner UNITED STATES PATENTS l Beebe et a1 96115 3,042,519 7/62 Wainer 9690 3,046,125 7/ 62: Wainer 96-90 3,056,673 =l0/6-2 Wainer 96--90 3,082,086 3/ 63 Sprague 9690 NORMAN G. TORCHIN, Primary Examiner. 

1. A COMPOSITION PRINTING OUT AN IMAGE DIRECTLY WHEN EXPOSED TO A SUITABLE DOSAGE OF ULTRAVIOLET, SAID IMAGE EXHIBITING RELATIAVELY GOOD BLUE ABSORPTION, SAID COMPOSITION BEING PHYSICALLY SUPPORTED IN AN INERT CARRIER AND SAID COMPOSITION CONSISTING ESSENTIALLY OF (1) AT LEAST ONE ORGANIC BROMINE COMPOUND SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS REPRESENTED BY THE GENERAL FORMULA
 11. THE PROCESS WHICH COMPRISES PREPARING THE COMPOSITION OF CLAIM 1 IN A THIN DRY LAYER, PHOTOGRAPHICALLY EXPOSING SAID COMPOSITION TO A DOSAGE OF ULTRAVIOLET RADIATION AND FIXING THE RESULTANT IMAGE BY HEAT. 